CN104797337A - An alumina silicate zeolite-type material for use as a catalyst in selective catalytic reduction and process of making thereof - Google Patents

An alumina silicate zeolite-type material for use as a catalyst in selective catalytic reduction and process of making thereof Download PDF

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CN104797337A
CN104797337A CN201380058685.9A CN201380058685A CN104797337A CN 104797337 A CN104797337 A CN 104797337A CN 201380058685 A CN201380058685 A CN 201380058685A CN 104797337 A CN104797337 A CN 104797337A
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zeolite
stt
type
modification
catalyst
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CN104797337B (en
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M·曼卡
李运奎
J·拉沙佩勒
武炜
D·谢泼德
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Pacific Industrial Development Corp
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Abstract

The present disclosure generally provides novel STT-type zeolite materials called PIDC- MM-0501, PIDC-MM-0502, and PIDC-MM-0805/0806 or PIDC-type zeolites and a method of making these zeolites. The present disclosure also provides for the use of these zeolite materials as a catalyst and a method of preparing said catalyst. The PIDC-MM-type zeolites or STT-type zeolite materials may be used as a catalyst, such as in Selective Catalytic Reduction (SCR) applications.

Description

Alumina silicate zeolite-type material and the manufacture method thereof of catalyst is used as in SCR
Invention field
Disclosure of the present invention relates in SCR (SCR) reaction, be used as catalyst alumina silicate or aluminosilicate zeolite-shaped material and the method forming described catalyst.
Background of invention
Explanation in this part only provides the background information about the disclosure of invention and can not form prior art.
Zeolite is a kind of crystal aluminosilicate with the three-dimensional network framework of extension based on oxonium ion.The basic structural unit of all zeolites is the tetrahedron surrounding little silicon or aluminum ions four oxygen anions.Arrange these tetrahedrons, to make in these four oxygen anions each itself share with another silica or alumina tetrahedra again.Crystal lattices extends in three-dimensional, and calculates the electric charge of each oxygen anion, and namely oxidation state is-2.Each silicon ion has its+4 electric charges, and this is by four tetrahedron oxygen anions balances, and therefore silicon-oxygen tetrahedron is electroneutral.Each aluminium tetrahedron has the residual charge of-1, because trivalent aluminium is bonded on four oxygen anions.This residual electric charge is by occupying non-frame position and serving as the cation balance in the Bronsted site of supply strong acid, this Molecular Sieves:Principles of Synthesis and Identification will being author in following schematic diagram and at R.Szostak, 2nd edition, Blackie Academic and Professional, London, further describes in 1998.
Typically by containing alkali metal or alkaline earth oxide source; The oxide source of silicon; Optionally alumina source; With by 1-amantadine, its derivative, N, N, N-trimethyl-1-adamantane ammonium hydroxide, and composition thereof derivative cationic aqueous reaction mixture, preparation is containing the zeolite of UZM-5 HS or molecular sieve.Fume colloidal silica is used as the Typical sources of Si oxide, and aluminium hydroxide is used as the Typical sources of aluminium oxide.Then " the former state synthesis " crystalline zeolite formed by crystallization can be further processed.Such as, by heat treatment (namely calcining), removing structure directing agent (SDA).This further process comprises use known method, such as, use rare acid solution or ammonium nitrate solution, remove metal cation by ion-exchange.
The people such as Y.Nakagawa at Microporous and Mesoporous Materials, 22 (1998), determined by calculating in 69-85 page and can use Ν, the zeolite that Ν, Ν-trimethyl-1-adamantamrnonium cation five kinds of manufacturing are different.Their molecular model calculates consistent with their experimental data.They reported this template and make SSZ-13, the crystallization of zeolites of SSZ-23, SSZ-24, SSZ-25 and SSZ-31 type.They show the crystalline field border of the five kinds of zeolites manufactured commonly by two SDA.Ν, Ν, Ν-trimethyl-1-adamantane ammonium SDA molecule makes chabasie in SAR 10-40 place's crystallization, and STT phase is in SAR 50-70 place's crystallization.Seldom there is organic formwork can produce the structure of SSZ-23.
Summary of the invention
Disclosure relate generally to of the present invention is called PIDC-MM-0501, the New type of S TT-type zeolitic material of PIDC-MM-0502 and PIDC-MM-0805/0806 or PIDC-MM-type zeolite, and manufactures the method for these zeolites.Disclosure of the present invention also provides these zeolitic materials as the purposes of catalyst and the method preparing described catalyst.Surprisingly, these new material structure occur as the product form under the synthesis condition of reaction type described herein and particular group.STT-type zeolitic material comprises and is greater than the mol ratio that about 19:1-is about the tetradic oxide of 250:1 and the oxide of triad, and feature can be the specific peak that exists in X-ray diffraction pattern.
The STT-type zeolitic material of PIDC-MM-type zeolite or modification can be used as catalyst, such as SCR application in as catalyst.For both ammonia and n-propylamine, what the temperature programmed desorb (TPD) on new PIDC-MM-shaped material was studied relatively shows, with known SSZ-13 zeolite facies ratio, they contain more highly acid site.In TPD measures, such as, by using the probe molecule with basic character, ammonia and n-propylamine, and measure temperature when they are desorbed, the acid strength of the zeolite synthesized by monitoring.
The method preparing zeolite-type material generally includes formation aqueous reaction mixture, and described aqueous reaction mixture comprises tetradic oxide source; The oxide source of triad; Alkali metal source; And Organic structure directing agent, described Organic structure directing agent comprise N at least partially, N, N-trimethyl-1-amantadine hydroxide; Maintain this aqueous mixture be enough under the crystallization condition making zeolite-type material crystal, thus demonstrate specific X-ray diffraction pattern; With this zeolite crystal of recovery.
Comprised the steps: to make zeolite-type material dealuminzation with nitric acid by the method for zeolite-type material Kaolinite Preparation of Catalyst, form the zeolite of dealuminzation; With the aqueous impregnation of slaine or the zeolite of this dealuminzation of ion-exchange; With will be selected from Cu, a kind of metal in Fe, Co, Zr, Ti or its mixture is incorporated in the framework position of dealuminated zeolite.
According to explanation provided herein, further application is apparent.Should be appreciated that description and specific embodiment are intended to the object just to setting forth, and be not intended to limit the scope of the disclosure of invention.
Accompanying drawing is sketched
The object of accompanying drawing described herein just to setting forth, and be definitely not intended to limit the scope of the disclosure of invention.
Fig. 1 is the schematic diagram of the STT zeolite preparing modification according to the instruction of the disclosure of invention;
Fig. 2 is the x-ray powder diffraction analysis spectrogram of the zeolite according to embodiment 1 preparation;
Fig. 3 is the x-ray powder diffraction analysis spectrogram of the burnt zeolite according to embodiment 1 preparation;
Fig. 4 is the x-ray powder diffraction analysis spectrogram of the zeolite according to embodiment 2 preparation;
Fig. 5 is the x-ray powder diffraction analysis spectrogram of the burnt zeolite according to embodiment 2 preparation;
Fig. 6 is the x-ray powder diffraction analysis spectrogram of the zeolite according to embodiment 3 preparation;
Fig. 7 is the x-ray powder diffraction analysis spectrogram of the burnt zeolite according to embodiment 3 preparation;
Fig. 8 is provided in synthesis (a) existing SSZ-13 (PIDC-801), (b) PIDC-MM-0501 zeolite-type material, and c) ESEM (SEM) image of product that obtains in PIDC-MM-0502 zeolite-type material;
Fig. 9 is the schematic diagram of TPD instrument;
Figure 10 is the diagram of the ammonia desorption curve demonstrated by the fresh zeolite sample prepared according to the instruction of the disclosure of invention;
Figure 11 be by by hydrothermal aging (750 DEG C 24 hours, 10%H 2the diagram of the ammonia desorption curve that zeolite sample O) demonstrates;
Figure 12 is the diagram of the n-propylamine desorption curve demonstrated by the fresh zeolite sample prepared according to the instruction of the disclosure of invention;
Figure 13 is the diagram of the n-propylamine desorption curve demonstrated by the zeolite sample by hydrothermal aging (750 DEG C 24 hours, have 10% steam);
The diagram of the n-propylamine that Figure 14 provides the zeolite sample prepared according to the instruction of the disclosure of invention to demonstrate and propylene desorption curve;
Figure 15 is the expanded view of the n-propylamine desorption curve demonstrated by the sample from the chart shown in Figure 14;
Figure 16 is the expanded view of the propylene desorption curve demonstrated by the sample from the chart shown in Figure 14;
Figure 17 is for the fresh Cu-PIDC-MM-type zeolite prepared according to the instruction of the disclosure of invention with at 750 DEG C, 10%H 2the NO of the hydrothermal aging zeolite sample of 24 hours at 200 DEG C under O xthe diagram of conversion ratio; With
Figure 18 is for the fresh Cu-PIDC-MM-type zeolite prepared according to the instruction of the disclosure of invention with at 750 DEG C, 10%H 2the NO of the hydrothermal aging zeolite sample of 24 hours at 500 DEG C under O xthe diagram of conversion ratio
Describe in detail
Following illustrative only exemplifies, and is not intended to limit absolutely disclosure of the present invention or its application or purposes.Should be appreciated that in the middle of description, corresponding reference marker refers to identical or corresponding parts and feature.
Disclosure of the present invention usually provides the STT zeolite-type material of modification, and it demonstrates the catalytic activity of reacting SCR (SCR).Demonstrate according to this zeolite-type material prepared by synthesis condition described herein the high catalytic activity being better than existing SSZ-13 type zeolite, this is proved by ammonia and n-propylamine temperature desorb research.Adopt the XRD reflection of the material of " former state synthesis ", at d=1.08 (7.8%); 0.837 (4.0); 0.845 (3.6); 0.480 (4.5); 0.456 (3.8); 0.445 (1.6); 0.416 (4.0); With 0.364 (2.6) nm place, observe and there is STT-type zeolite.The experience gel composition following formula of zeolite prepared by former state represents:
5.577 NaOH:4.428 RNOH:Al 2O 3:28 SiO 2:1219.7 H 2O
Provide following specific embodiments, set forth the preparation of the STT zeolite-type material of the modification prepared according to the instruction of the disclosure of invention, qualification and purposes, and should not be interpreted as the scope limiting the disclosure of invention.In view of disclosure of the present invention, it will be understood by those skilled in the art that, many changes can be made in specific embodiments disclosed herein, and when not departing from or exceed the spirit or scope of the disclosure of invention, still obtain same or similar result.Those skilled in the art will be further understood that, any performance representative reported herein is measured and the performance obtained by multiple distinct methods routinely.Method described herein represents under the ambit not exceeding the disclosure of invention, a kind of available such method and additive method.
With reference to figure 1, generally by reaction stirred, until obtain uniform milky solution, the STT zeolite-type material of the modification of the preparation disclosure of invention.In 2.0L Parr autoclave, at 150 DEG C-160 DEG C, carry out the synthesis 4-7 days of zeolite crystal.Once cooling, then the content of reactor vessel is poured in filter, and washs this crystal with distilled water, and at 120 DEG C dried overnight.After composition, before ion-exchange, calcined zeolite, to remove zeolite framework structure directing agent.
" the former state synthesis " crystalline zeolite formed by crystallization can be further processed.Such as, by heat treatment (that is, calcining), removing template or structure directing agent (SDA).This further process also can comprise by any method well known by persons skilled in the art, comprising, but be not limited to, use the method for diluted acid or ammonium nitrate solution, by ion-exchange, removing metal cation.
Can by the ion exchange technique of standard, such as, in U.S. Patent No. 3,140,249, U.S. Patent No. 3,140,251, and U.S. Patent No. 3,140, in 253 describe those, by replacing some existing cations with metal cation, metal is incorporated in zeolite.Typical cation replaces the metal cation that can comprise and use and be selected from periodic table in 1-12 race and composition thereof, the element of the 1st, 2 and 8 races in preferred cycle table.
The zeolite with the transition metal be incorporated in framework demonstrates difference and very valuable catalytic activity.Such as, the past, the zeolite containing cobalt was very interested theme for many years, and this is mainly because they have catalytic performance with in methane selectively catalytic reduction (SCR) nitrogen oxide.This reaction is important, because expection methane substitutes ammonia as the NO discharged from static father xreducing agent.The U.S. announces No.2008/0226545A1 and discloses in wide temperature range, uses the selective catalyst reduction of nitrogen oxides by ammonia, and the zeolite that copper exchanges discharges NO in control from gaseous medium xpurposes.
The key factor affecting the catalytic activity of zeolite catalyst is the syntheti c route for this catalyst choice.Such as, the people such as Janas at Applied Catalysis B:Environmental, 91, (2009), describe at SCR (SCR) NO in the 217th page xin, copper content is on the impact of the catalytic activity of copper β zeolite (CuSiBEA).By two step post-synthesis, copper can be controlled and be incorporated in the framework of β zeolite, obtain CuSIBEA catalyst.
Products therefrom is characterized by XRD.Use the step-length of 0.02 ° of 2 θ, from 2 θ of 5 to 35 °, obtain pattern.Use Carl-Zeiss microscope, obtain ESEM (SEM) image and Energy Dispersive X-ray spectroscopic methodology (EDAX) chemical analysis.Study in the enterprising trip temperature desorb of 2920Micromeritics instrument be coupled with MKS Cirrus mass spectrograph.The material of all synthesis is white powder.
The method of the disclosure of invention provides the synthetic method of metallic modification STT-type zeolite, silica prepared by its former state with 28:1 and alumina molar ratio, and mixes metal, such as copper, iron, cobalt, zirconium, titanium or its mixture are in the framework position of this dealuminzation silica.The method comprises the steps:, and (1) makes zeolite dealumination with nitric acid, and then (2) use the aqueous solution of slaine, such as Cu (NO 3) 2h 2the zeolite of O solution impregnation gained dealuminzation.Metal cation from this metal salt solution to occupy in zeolite framework in advance by site that aluminium (Al) cation occupies.The method optionally comprises the steps: that the STT-type zeolite of heat modification is at least 150 DEG C, or the temperature of about 160 DEG C after flooding with aqueous metal salt.The amount of metal scope existed in the STT-type zeolite of metallic modification is about 0.3-about 10.0%, or about 0.3-about 3.3%, based on the gross weight of the STT-type zeolite of metallic modification.The cell size of this zeolite framework is typically less than about 6 nanometers.
According to the another aspect of the disclosure of invention, be provided in the preparation method of the STT-type zeolite of the modification used in the preparation of the STT-type zeolite catalyst of metallic modification.The method usually provides (A): the mol ratio of (B) is greater than the modification STT-type zeolite of about 19:1, and wherein (A) is the oxide of quadrivalent element oxide, and (B) is the oxide of triad.The method comprises formation aqueous reaction mixture, and described aqueous reaction mixture comprises (A) source; (B) source; Alkali metal cation source; With Organic structure directing agent (SDA), wherein SDA comprises Ν at least partially, Ν, Ν-trimethyl-1-amantadine hydroxide; Maintain this aqueous reaction mixture be enough under the crystallization condition forming STT-type zeolite crystal, and reclaim the STT-type zeolite crystal of modification.
Alkali metal cation source is preferably alkali metal hydroxide, and alkali metal cation is a part for the crystalline oxide materials of former state synthesis, and then balance valence electron electric charge within it.Such as, quadrivalent element can be silicon, and (A) source is water content is the fume colloidal silica of about 2wt%, and triad can be aluminium, and (B) source is the aluminium hydroxide that water content is less than or equal to the drying of about 63%.The cell size of gained zeolite is typically less than about 6nm.
Still with reference to figure 1, can be used as catalyst according to zeolite-type material prepared by the instruction of the disclosure of invention, such as, in SCR application, be used as catalyst.By having the probe molecule of basic character, such as ammonia and n-propylamine, the temperature (temperature programmed desorb measuring method) when being desorbed by measuring them, the acid strength of the zeolite sample synthesized by monitoring.The desorb temperature programmed by ammonia and n-propylamine-TPD technology, measure the acidity of sample.Optionally, can at honeycomb, comprising wall-flow type substrate (wall flow substrate), metallic substrates, or extrude on substrate or extrudate and deposit metallic catalyst.
The SCR activity of zeolite catalyst can be increased with the aluminium of Cu, Fe, Co, Zr, Ti or the zeolite structured inside of its mixture replacing.The modification STT-type zeolite in framework lattice with metal can store less ammonia.This metal replaces process can be reduced in the bronsted acid sites amount existed in catalyst, and substitutes these sites with Lewis-acid sites.Metal substitute can be reduced in the NO occurred in ammonia SCR catalyst generally xleakage (slip).
Embodiment 1-synthesizes the STT-type zeolitic material of PIDC-MM-0501 modification.
Combining hydrogen oxidation sodium solution and N, N, N-trimethyl-1-amantadine hydroxide.Regulate aluminium hydroxide, then silica Aerosil 200.Deionized water is added in obtained mixture.Reaction stirred, until obtain uniform milky solution.Gained slurries to be transferred in 2.0L Parr rustless steel container and to seal this container.This reactor vessel 6 days is heated for preparation PIDC-0501 zeolitic material at 160 DEG C.Once cooling, then topple over the content of reactor vessel in filter, and use distilled water washing crystal, and at 120 DEG C dried overnight.After composition, calcined zeolite powder before ion-exchange, so that the frame structure directed agents removing zeolite.
Outline in table 1 below, and show the X-ray diffraction pattern of the PIDC-MM-0501 zeolite product obtained by this operation in figs 2 and 3.Prepared zeolite comprises the mixture of SSZ-13 and SSZ-23 phase.In X-ray diffraction pattern, following 2 θ: 8.22,9.68,14.51,15.55,17.9,18.58,19.3,19.66,21.5, and each peak at 27.4 places is owing to there is SSZ-23 phase, and other peaks are owing to there is SSZ-13 phase.
The x-ray data (embodiment 1) of table 1.PIDC-MM-0501
Embodiment 2-synthesizes the STT zeolite-type material of PIDC-MM-0502 and PIDC-MM-0805/0806 modification
Combining hydrogen oxidation sodium solution and N, N, N-trimethyl-1-amantadine hydroxide.Add aluminium hydroxide, then silica Aerosil 200.Deionized water is added in gained mixture.Stir this reactant, until obtain uniform milky solution.Gained slurries to be transferred in 2.0L Parr rustless steel container and to seal this container.This reactor vessel is heated 7 days at 160 DEG C.Once cooling, then topple over the content of reactor vessel in filter, and use distilled water washing crystal, and at 120 DEG C dried overnight.Heating-up temperature, the change that temperature is surged and the JND of crystallization process causes pattern slight, thus cause PIDC-MM-0502 and PIDC-MM-0805/0806 zeolitic material.After composition, calcined zeolite powder before ion-exchange, so that the frame structure directed agents removing zeolite.
Provide X-ray diffraction (XRD) pattern of the PIDC-MM-0502 zeolite product obtained by this operation in figures 4 and 5.XRD analysis shows that this zeolite is by these two phase compositions of SSZ-13 and SSZ-23, wherein at the peak at following 2 θ places owing to SSZ-23 phase: 8.22,9.68,14.51,15.55,17.9,18.58,19.3,19.66,21.5, and 27.4, and other each peak is owing to SSZ-13 phase.Find that X-ray diffraction (XRD) pattern of PIDC-MM-0502 material is in this embodiment similar to PIDC-MM-0501 material (see embodiment 1), difference increases owing to the relative intensity at the peak of SSZ-23 phase.The increase of this peak intensity causes in the longer reaction time, and the longer reaction time is conducive to the crystallization of SSZ-23 zeolite facies.
The pure SSZ-13 (PIDC-0801) that embodiment 3-synthesis is conventional
Combining hydrogen oxidation sodium solution and N, N, N-trimethyl-1-amantadine hydroxide.Add aluminium hydroxide, then silica Aerosil 200.Deionized water is added in gained mixture.Stir this reactant, until obtain uniform milky solution.Gained slurries to be transferred in 2.0L Parr rustless steel container and to seal this container.This reactor vessel is heated 4 days at 150 DEG C.Once cooling, then topple over the content of reactor vessel in filter, and use distilled water washing crystal, and at 120 DEG C dried overnight.After composition, calcined zeolite powder before ion-exchange, so that the frame structure directed agents removing zeolite.
Provide the X-ray diffraction group of the Conventional zeolites product obtained by this operation in figs. 6 and 7.The difference observed between the Conventional zeolites prepared in an embodiment and the zeolite of the disclosure of invention there is peak at following 2 θ degree places: 8.22,9.68,14.51,15.55,17.9,18.58,19.3,19.66,21.5, and 27.4, this is owing to occurring SSZ-23 phase.These peaks are not present in the XRD pattern of the conventional SSZ-13 zeolite prepared in this embodiment.
Refer now to Fig. 8, relatively in the synthesis existing SSZ-13 of (A) embodiment 3-(CHA), (B) embodiment 1-PIDC-0501 zeolite-type material, and ESEM (SEM) image of the product obtained in (C) embodiment 2-PIDC-MM-0502 zeolite-type material.In fig. 8 a, existing SSZ-13 zeolite demonstrates the cubic shape that particle mean size is the typical chabasie of 2-10 μm.Such as, but in the fig. 8b, PIDC-MM-0501 material demonstrates the mixture of cubic nonlinearity spheric granules, club.In Fig. 8 C, PIDC-MM-0502 material also demonstrates the mixture of cubic nonlinearity spheric granules.In this accompanying drawing, the surface aggregation of spheric granules has cubic crystal.Therefore, the material (Fig. 8 B and 8C) prepared according to the disclosure of invention demonstrates and indicates the isometric particle that the indication SSZ-13 of the spheric granules eutectic that SSZ-23 is zeolite structured is zeolite structured.The STT-type zeolitic material of modification has the granularity that D50 is about 0.1-50 micron.
The desorb that embodiment 4-is temperature programmed
Adopt alkali molecules NH 3with the temperature programmed desorb of n-propylamine, study at existing SSZ-13, and the gross properties of acidic site and distribution on the PIDC-MM zeolite-type material prepared herein.On the 2920Micromeritic instrument be connected with the thermal conductivity detector (TCD) in MKS Cirrus Mass Spec equipment, record TPD spectrum.Figure 9 illustrates schematic diagram.
Typically, for NH 3-TPD, at 500 DEG C, under the speed of 20 DEG C/min, at 25mL min -1helium flow in, pretreatment 0.1g catalyst 30 minutes, is then cooled to the desorption temperature of 100 DEG C.Ammonia (10% ammonia/90% argon gas) this catalyst saturated of use dilution at 100 DEG C 30 minutes.After saturation, at 25mL min -1under, with helium purification sample 20 minutes, to remove the ammonia of faint absorption on the zeolite surface.Then, under the rate of heat addition of 20 DEG C/min, adopt at 25mL min -1the flowing helium of lower maintenance, raises sample temperature to 650 DEG C from 100 DEG C, finally keeps 40 minutes at 650 DEG C.Use mass spectrograph, the NH of monitoring desorb 3.
Typically, for n-pro-pyl-TPD, at 500 DEG C, at 25mL min -1helium flow in, pretreatment 0.1g catalyst 30 minutes, is then cooled to the desorption temperature of 100 DEG C.At 60 DEG C, the flask of heating containing n-propylamine, generates n-propylamine steam.(dose) is fed intake to catalyst with the n-propylamine of dilution.Repeatedly feed intake, until sample is saturated, this is by peak evidences such as existence 5.After saturation, at 25mL min -1under, with helium purification sample 20 minutes, to remove the ammonia of faint absorption on the zeolite surface.Then, under the rate of heat addition of 20 DEG C/min, raise sample temperature to 650 DEG C from 100 DEG C, the helium simultaneously flowed is 25mLmin -1.Use mass spectrograph, the n-propylamine of monitoring desorb.
By their TPD peak area, evaluate the ammonia amount (Figure 10) from desorb these three samples.There are two NH 3desorb peak.NH at about 160 DEG C 3desorb peak is relevant with weak acid site, with relevant with strong acid site at another peak higher than 480 DEG C of places.This three kinds of zeolite PIDC-MM-0501, PIDC-MM-0502 and PIDC-0801 (routine) demonstrate different acidity.Figure 11 illustrates the ammonia desorption curve of the zeolite sample of hydrothermal aging.For fresh and aging both samples, compared with pure SSZ-13, the desorption performance of new PIDC zeolite-type material is significantly higher.As shown in table 2, the desorption ability of ammonia increases in the following sequence on these samples: PIDC-0801 (routine) <PIDC-MM-0501<PIDC-MM-0502.
Table 2
Lot#PIDC-MM Acidity (mmol/g) Desorption temperature
0501 0.77 493.3
0502 1.065 512
0801 (routine) 0.768 474
For fresh sample in Figure 12 and 14, and in Figure 13, respectively illustrate the result of n-propylamine TPD curve for aged samples.All samples demonstrates two desorb peaks at 160 DEG C and 380 DEG C of places, and the n-propylamine that this hint exists two energy active types on these samples absorbs site, represents acidity and the propylene acidity of n-propylamine).The desorb peak of higher temperature is attributable to the n-propylamine interaction stronger with the silanol group existed in the surface of zeolite sample.The absorbent properties of the PIDC-MM zeolite-type material of the disclosure of invention are significantly higher than existing or conventional SSZ-13.
For the curved portion corresponding with n-propylamine acidity, provide the expanded view of the desorption curve from Figure 14 in fig .15, and for the curved portion corresponding with propylene acidity, provide the expanded view of the desorption curve from Figure 14 in figure 16.In these two curves, the absorption of the PIDC-MM zeolite-type material of the disclosure of invention is significantly higher than the absorption of existing or conventional SSZ-13.In fact, the propylene amount (area under a curve in figure 16) obtained by desorb is corresponding to 1.61mmol/g SSZ-13 material), and PIDC-MM-0805, PIDC-MM-0502,2.86 are demonstrated with PIDC-MM-0806 zeolite-type material, 3.48, and 4.27mmol/g zeolitic material.Therefore, PIDC-MM zeolite-type material demonstrates the bronsted acid sites of larger quantity, and bronsted acid sites is more remarkable than the site existed in SSZ-13 zeolitic material stronger.In fact, these bronsted acid sites cause demonstrating and SSZ-13 zeolite facies ratio, the zeolite-type material that the increase of n-propylamine temperature desorb is greater than 50%.
Use the Micromeritics 2920 that serves as microflow reactor and through after sample, carry out the MKS residual gas analyzer of gas concentration analysis, test NO xconversion ratio.Adopt following gas concentration, test sample: NO=175ppm; NO 2=175ppm; NH 3=350ppm; And O 2=175ppm.50,000 -1under the space velocity of/hr, test sample.By calculating NO by the limit after MKS residual gas analyzer 45 minutes under a constant xconversion values.Respectively in fig. 17 for fresh sample with show NO for aged samples in figure 18 xthe result of conversion ratio.After aging under 200 DEG C and 550 DEG C of these two temperature, NO xconversion ratio declines.The NO of fresh catalyst at about 200 DEG C xconversion ratio performance is 75%, and is about 70% at about 500 DEG C.For the catalyst of hydrothermal aging, the NO of catalyst at about 200 DEG C xconversion ratio performance is 30%.For the catalyst of hydrothermal aging, the NO of catalyst at about 500 DEG C xconversion ratio performance is 35%.NO xthis decline of conversion ratio proves loss of activity, and this loss sample acidity reduction after being exposed to hydrothermal aging conditions causes.
In order to the object set forth and describe lists aforementioned explanation of the present invention and various forms.And be not intended to be exhaustive or to limit the invention in disclosed precise forms.In view of above-mentioned instruction, many modifications or change are possible.Select and describe discussed form, to provide the preferably elaboration of the principle of the invention and practical application thereof, thus making those of ordinary skill in the art can in a variety of manners and under various modification, utilize the present invention, because they are suitable for considered special-purpose.All this modifications and change in the scope of the invention that claims are determined, when fair according to them, during the width explanation of legal and just mandate.

Claims (28)

1. one kind is used as the modification STT-type zeolitic material of the crystallization of catalyst, this modification STT-type zeolitic material comprises mol ratio and is greater than the tetradic oxide of about 19:1 to about 250:1 and the oxide of triad, and has the peak in X-ray diffraction pattern as shown in Figure 3.
2. the modification STT-type zeolitic material of claim 1, wherein in X-ray diffraction pattern, at the peak at following 2 θ degree places owing to there are SSZ-23 zeolite facies: 8.22,9.68,14.51,15.55,17.9,18.58,19.3,19.66,21.5, and 27.4.
3. the modification STT-type zeolitic material of claim 1 and 2, wherein the mol ratio of the oxide of tetradic oxide and triad is about 19:1 to 50:1.
4. the modification STT-type zeolitic material of claim 1-3, wherein experience gel composition following formula represents:
5.577 OH：4.428 RNOH：Al 2O 3：28 SiO 2：1219.7 H 2O。
5. the modification STT-type zeolitic material of claim 1-4, wherein this zeolite-type material comprises a kind of metal be selected from copper, iron, cobalt, zirconium, titanium and composition thereof further.
6. the modification STT-type zeolitic material of claim 5, wherein metallic zeolite-type material serves as catalyst in SCR (SCR) reaction.
7. the modification STT-type zeolitic material of claim 5-6, the range of metal wherein existed in this catalyst is 0.3-10.0%, based on the gross weight of this zeolite catalyst.
8. the modification STT-type zeolitic material of claim 1-7, wherein the feature of this zeolite-type material is the desorb of ammonia temperature and the desorb of n-propylamine temperature respectively than large at least 1.4 and 2.0 times of the desorb of corresponding SSZ-13 zeolite.
9. the modification STT-type zeolitic material of claim 1-8, wherein the feature of the zeolite-type material of hydrothermal aging is the desorb of ammonia temperature and the desorb of n-propylamine temperature respectively than large at least 1.5 and 6.5 times of the desorb of corresponding SSZ-13 zeolite.
10. the modification STT-type zeolitic material of claim 5, wherein this catalyst contains the Ni metal of ion-exchange, Fe, Co, Zr, Ti, and it is enough to the NO maintained in the waste gas streams of nitrogen-containing oxide xconversion ratio performance.
The modification STT-type zeolitic material of 11. claims 10, the wherein NO of fresh catalyst at about 200 DEG C xconversion ratio performance is 75%.
The modification STT-type zeolitic material of 12. claims 11, the wherein NO of fresh catalyst at about 500 DEG C xconversion ratio performance is about 70%.
The modification STT-type zeolitic material of 13. claims 10, wherein at about 200 DEG C, for the catalyst of hydrothermal aging, the NO of this catalyst xconversion ratio performance is 30%.
The modification STT-type zeolitic material of 14. claims 13, wherein at about 500 DEG C, for the catalyst of hydrothermal aging, the NO of this catalyst xconversion ratio performance is 35%.
The modification STT-type zeolitic material of 15. claim 5-14, wherein metallic zeolite is deposited on the extrudate of honeycomb, metallic substrates or shaping.
The modification STT-type zeolitic material of 16. claims 15, wherein honeycomb substrate comprises wall-flow type substrate.
The modification STT-type zeolitic material of 17. claim 1-16, wherein this zeolite-type material has the granularity that D50 is about 0.1-50 micron.
18. 1 kinds of methods preparing metallic catalyst, the method comprises the steps:
Zeolite dealumination is made with nitric acid;
With aqueous metal salt dipping or the zeolite of this dealuminzation of ion-exchange; With
To be selected from Cu, the metal in a kind of or its mixture in Fe, Co, Zr, Ti is incorporated in the framework position of the zeolite of dealuminzation.
The method of 19. claims 18, wherein catalyst is incorporated in metal in framework, and its content is enough to the NO maintained in the waste gas streams of nitrogen-containing oxide xconversion ratio performance.
The method of 20. claim 18-19, wherein the method is included in further in honeycomb substrate, metallic substrates or the substrate of extruding and deposits this catalyst.
The method of 21. claims 20, wherein this honeycomb substrate comprises wall-flow type substrate.
The method of 22. claim 18-21, the method comprises further and prepares zeolite, and the mol ratio making it have the oxide of tetradic oxide and triad is greater than about 19:1, and described zeolite is prepared by following step:
Form aqueous reaction mixture, described aqueous reaction mixture comprises tetradic oxide source; The oxide source of triad; Alkali metal source; And Organic structure directing agent, described Organic structure directing agent be N, N, N-trimethyl-1-amantadine hydroxide at least partially;
Under being enough to make the condition of zeolite-type material crystal structure, maintain this aqueous mixture, described crystal has the X-ray diffraction figure provided in Fig. 2; With
Reclaim this zeolite crystal.
The method of 23. claims 22, the wherein fume colloidal silica of tetradic oxide source to be water content be about 2wt%.
The method of 24. claims 22, wherein the oxide source of triad is aluminium hydroxide.
The method of 25. claim 22-24, wherein alkali metal cation is equilibrated at the valence electron electric charge in crystalline zeolite-shaped material.
The method of 26. claim 18-25, wherein the method comprises heating zeolite further to the temperature of at least 150 DEG C.
The method of 27. claims 26, wherein heating zeolite is to the temperature of about 160 DEG C.
The modification STT-type zeolitic material of 28. claim 1-7, wherein the feature of this zeolite-type material is that bronsted acid sites is better than this site in SSZ-13 zeolite and the quantity of depositing is greater than this site in SSZ-13 zeolite;
Wherein bronsted acid sites causes demonstrating and SSZ-13 zeolite facies ratio, the zeolite-type material that n-propylamine temperature desorb increase is greater than 50%.
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